Beloit College > Chemistry > Nanochemistry

Chemistry plays a significant role in the emerging interdisciplinary fields of nanoscience and nanotechnology. The nanoscale refers to materials with dimensions on the scale of nanometers (a thousandth of a thousandth of a thousandth of a meter). Control of the material world at the scale of atoms and molecules can produce materials with fundamentally different properties and behavior and has been touted as the next technological revolution. Some questions we will consider include: What nanotechnology already exists? What makes nanomaterials special? How can they be prepared? What tools can be used to study such materials? Three class periods and one laboratory period per week. (U) Offered each spring.

Prerequisite: Some chemistry or physics background.


Spring 2018
Nanochemistry
Lisensky

 First Half

Jan 22 Class: Nanochemistry Basics
Jan 24 Discussion of Reading: Concepts of Nanochemistry, Introduction (pages 1-10).
Discussion of Reading: Nanotech Promise (2007) by Peterson and Heller from Nanoethics: The Ethical and Social Implications of Nanotechnology.
Discussion of Reading: The invisible giant: a future enabled by nanotechnology (2013), Section 1.2 in European Commission Nanotechnology Report.
Discussion of Video: Water filter (2015) from Liquidity Nanotech (youtube)
Discussion of Video: Filtering Drinking Water with Nanofibers (2016) from MIT Technology Review or youtube.
Skim: "Electrochromic energy storage devices," Materials Today, September 2016, 394-402.
Lab: Electrochromic Prussian Blue Thin Films. See required lab notebook format and using our multimeters.
Jan 26 Literature reports 1A
Choose a recent nano article from Nanoletters or ACS Nano. Summarize the paper in a short oral report, focusing primarily on a figure or two in the paper. Be sure to check for supplementary information (movies and the experimental section may be located there). By end of Wednesday email to claim a paper by including a link to the abstract. Papers that have been selected will be posted here. Your article grade will be based on whether you understand the selected material so select something you understand. Test questions in this course will be drawn from these student selected papers, so for the rest of the class your presentationis a practice test.
1. Evans: "Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures" (2018)
2. Pearlman:"Graphene-based bimorphs for micron-sized, autonomous origami machines", (2018) Vimeo
3. Kelly: "Nanoscale Control of Molecular Self-Assembly Induced by Plasmonic Hot-Electron Dynamics" (2018)
4. Camacho: "Reversibly Bound Kinesin-1 Motor Proteins Propelling Microtubules Demonstrate Dynamic Recruitment of Active Building Blocks" (2018) Kinesin
   
Jan 29 Class: Consumer Products
Lab notebook due for Electrochromic Prussian Blue. See required lab notebook format.
Jan 31 Discussion of Reading: Concepts of Nanochemistry, Concepts (Chapter 1).
Discussion of Reading: "Superhydrophobic and superoleophobic properties in nature," Materials Today, June 2015, 273-285.
Discussion of Video: Nasturtium Leaves (2013).
Discussion of Video: Lotus Effect (2011) or Australian Broadcasting Corporation.
Discussion of Video: Non-Stick Nanocoating for Efficient Shipping (2011) or EU Research Media Center or youtube.
Discussion of Video: Anti-icing Superhydrophobic coating (2009) or youtube.
Lab: Octadecanethiol Monolayer on Silver (main experiment, do this first) and Microcontact Printing of Thiols (an extension of the main experiment but begin the PDMS preparation while the ethanol is evaporating in the main experiment.)
Movie: Background information (self assembly)
Feb 2 Literature reports 1B
1. Christian: Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X=Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut (2015)
2. Zhang: Protein Handshake on the Nanoscale: How Albumin and Hemoglobin Self-Assemble into Nanohybrid Fibers (2018)
3. Dahlberg: Rapid Three-Dimensional Printing in Water Using Semiconductor–Metal Hybrid Nanoparticles as Photoinitiators (2017)
4. Valuck: Tau-Targeted Multifunctional Nanocomposite for Combinational Therapy of Alzheimer’s Disease (2018)
   
Feb 5 Class: Metal Nanoparticles
Lab notebook due for Silver Thiol.
Feb 7 Discussion of Reading: Concepts of Nanochemistry, Gold (Chapter 3).
Skim: Crystal structures of gold nanoparticles (jmol).
Discussion of Video: Gold Nanoshells, Synthesis and Demonstration (2009) or youtube.
Discussion of Video: Synthesis of Hollow Gold Nanospheres (2010) or youtube.
Skim: Science Translational Medicine, 27 October 2010 or NIH.
Skim: Rice team achieves a cancer milestone, Houston Chronicle, November 2012.
Skim: Solar Vapor Generation Enabled by Nanoparticles, ACS Nano, 7(1), 42-49 (2013).
Skim: Using Gold Nanoparticles to Kill Cancer, Physics Central, APS, April 2016 and movie.
Skim: Exploding nanobubbles can kill cancer cells, Science, AAAS, February 2016.
Discussion of Reading: Liposuction Goes Nano, C&E News, June 16, 2014, 32-33.
Skim: Gold Nanoparticle-assisted Selective Photothermolysis of Adipose Tissue, Plast. Reconstr. Surg. Global Open, December 2014, 2(12) e283.
Lab: Three Syntheses of Gold Nanoparticles and Sodium Borohydride Synthesis of Silver Nanoparticles and Microwave-assisted Synthesis of Silver Nanoparticles. Write up the five syntheses with five different purpose, method, and actions and observations sections, each on a different page of your notebook. Since you will be doing five syntheses you can only spend 30 minutes on each. Write a combined conclusion section for the five experiments in which you answer the questions as you summarize and make comparisons.
Feb 9 Literature reports 1C
1. Simmons: "Low-Temperature Copper Bonding Strategy with Graphene Interlayer" (2018)
2. Knapp: "Laser-Induced Conversion of Teflon into Fluorinated Nanodiamonds or Fluorinated Graphene" (2018)
3. Tumicelli: "An Epidermis-like Hierarchical Smart Coating with a Hardness of Tooth Enamel" (2018)
4. Harrison: "A Facile Space-Confined Solid-Phase Sulfurization Strategy for Growth of High-Quality Ultrathin Molybdenum Disulfide Single Crystals" (2018)
   
Feb 12 Class: Nanowires
Lab notebook due for Gold and Silver Nanoparticles, five syntheses with one conclusion.
Feb 14 Discussion of Reading: “Nanoparticles Probe Biosystems,” Materials Today, Feb 2004, 36-43.
Discussion of Reading: “Directed assembly of nanowires,” Materials Today, May 2009, 34-43.
Discussion of Reading: “Programming Assembly," Inorg. Chem. 39, 2258 (2000).
Discussion of Reading: “Nanowires made from silver are super stretchy," Nature Materials, 16, p. 439–445 (2017).
Discussion of Video: Chad Mirkin (2009) or youtube.
Discussion of Video: Gold Nanoparticles or NOVA "Making Stuff: Smaller" (2011) or youtube.
Lab: Synthesis of Nickel Nanowires. You should get as far as obtaining the XRD in the filter or at least leaving the labeled sample to be run. Watch at least one XRD sample so you will know how to use the instrument next week.
Feb 16 Literature reports 2A
1. Evans: "In Situ Investigation of Defect-Free Copper Nanowire Growth"
2. Pearlman: "Peptide-Functionalized Phase-Transformation Nanoparticles for Low Intensity Focused Ultrasound-Assisted Tumor Imaging and Therapy" (2018)
3. Kelly: "Laser-Induced Graphene by Multiple Lasing: Toward Electronics on Cloth, Paper, and Food" (2018)
4. Camacho: "Air-Stable Anisotropic Monocrystalline Nickel Nanowires Characterized Using Electron Holography" (2018)
   
Feb 19 Class: Photonics
No lab notebook due
Feb 21 Discussion of Reading: Concepts of Nanochemistry, Silica (Chapter 2).
Skim: “Nanostructure Polymers for Photonics,” Materials Today, April 2008, pages 48-56.
Discussion of Reading: “P-Ink and Elast-Ink,” Materials Today, July 2008, pages 44-51.
Discussion of Reading: “Smelling chemicals with a photonic nose,” SPIE (2011).
Skim: Opalux Products (2015).
Discussion of Reading: “Keeping Good Company with the Chameleon,” Materials Views (2015).
Skim: “Electronic Qubit Integrated Into Solid-State Switch,” or IEEE Spectrum, 12 Feb 2016.
Skim: “Plasmonics Make Electrochromic Polymers Fast Enough for Video,” or IEEE Spectrum, 28 April 2016.
Skim: “Brighter Displays Come From the Wings of a Butterfly,” or IEEE Spectrum, 3 June 2016.
Discussion of Reading: “Nanophotonic Crystals Separate Real Luxury Watches From the Fakes,” or IEEE Spectrum, 28 June 2016.
Skim: “Flexible and Colorful Electronic Paper Promises a New Look for E-books,” or IEEE Spectrum, 18 October 2016.
Discussion of Video: NatureTech: The Material World, (2006) BBC Part 4 or youtube.
Discussion of Video: Operating Opalux P-Ink Device with a Battery (2010) or youtube.
Discussion of Video: Biomimicry, (2015) General Electric or youtube.
Discussion of Reading: "How to get that old-fashioned light bulb glow without wasting so much energy," Science, 2016.
Lab: Begin PMMA Nanospheres - Synthesis first so you can be sure to get to the after the synthesis part today. You will work in one of four groups. Write purpose and method just for today's lab work.
Lab: Finish Nickel Nanowires during the 40 minute PMMA reaction. Obtain free nanowire XRD and do visible microscopy to prepare labeled SEM sample.
Feb 23 Literature reports 2B
1. Christian: "Transient Clustering of Reaction Intermediates during Wet Etching of Silicon Nanostructures"
2. Zhang: "Self-Formed Hybrid Interphase Layer on Lithium Metal for High-Performance Lithium–Sulfur Batteries"
3. Dahlberg: "Highly Surface-Active Ca(OH)2 Monolayer as a CO2 Capture Material"
4. Valuck: "Highly Sensitive Bulk Silicon Chemical Sensors with Sub-5 nm Thin Charge Inversion Layers"
   
Feb 26 Class: Semiconductors, Metal Oxides, and Piezoelectricity
Feb 28 Discussion of Reading/Audio: Self-Cleaning Glass (2009) from The Naked Scientists.
Discussion of Video: Self-Cleaning Buildings (2012) or EU Research Media Center or youtube.
Discussion of Video: Smog-Eating Buildings (2013) or CNN or youtube.
Skim: “ZnO – nanostructures, defects, and devices,” Materials Today, May 2007, pages 40-48 but skip the defect section.
Discussion of Reading: “Progress in nanogenerators for portable electronics,” Materials Today, Dec 2012, pages 532-543.
Discussion of Reading: “Titanium Dioxide Nanoparticles in Food and Personal Care Products,” ES&T, 2012, 46(4), 2242–2250.
Discussion of Reading: “Activists take aim at nanomaterials in Dunkin Donuts” (2014).
Discussion of Reading: “Dunkin Donuts to remove titanium dioxide from donuts” (2015).
Skim: "Metal oxide nanowire chemical sensors: innovation and quality of life," Materials Today, December 2016, 559-567.
Lab: Start Hydrothermal Growth of ZnO Nanorods synthesis (10 minutes). Groups of four should set up the synthesis with two slides and leave in oven until next week. The actions and observations for the synthesis should be in your notebook. Leave the prepared tubes next to the oven for inspection.
Lab: Continue PMMA Nanospheres - Synthesis of Inverse Opal Photonic Crystals. The samples you saved in microcentrifuge tubes last week will already be centrifuged for several hours. Carefully remove the liquid and leave sample to dry (no vacuum chamber).
Lab: Continue PMMA Nanospheres - Optical Diffraction and SEM Determination of Particle Size. You did the dilution step last week. Set up the constant temperature evaporation.
Lab: Continue PMMA Nanospheres - Stokes Law measurements. Photograph needed every 3 or 4 days that includes the full tape height as scale. Measure distances using ImageJ. Do you need to start a new tube?
Mar 2 Literature reports 2C
1. Simmons
2. Knapp
3. Tumicelli
4. Harrison
   
Mar 5 Class: Field Effect Transistors
Lab notebook due for Nickel Nanowires.
Mar 7 TEST
Lab: Finish ZnO Nanorods measurements. In each group of four, one pair will do XRD and PEC measurements on one slide, and the other pair will do SEM and MB measurements on the other slide. For actions and observations you only need the two measurements you did, but data, graphs and conclusions will require you to exchange data and include the results from all four measurements on your duplicate slides.
Lab: Continue PMMA Nanospheres - Stokes Law measurements. Data needed every 3 or 4 days. Show instructor your graph to see if you need to start a new tube.

 Second Half

Mar 9 Literature reports 3A
1. Evans
2. Pearlman
3. Kelly
4. Camacho
Topic selection for March 24 due.
   
Mar 19 Class: Carbon Nanotubes
No lab notebook due (but work on ZnO since lab work is finished.)
Mar 21 Discussion of Reading: Concepts of Nanochemistry, Carbon (Chapter 7).
Discussion of Reading: “Toxicity of single-walled carbon nanotube: How we were wrong?,” Materials Today, January 2010, pages 6-8.
Discussion of Reading: “Carbon nanomaterials for high performance supercapacitors,” Materials Today, July 2013, pages 272-280.
Discussion of Reading: “Ultracentrifugation of single-walled nanotubes,” Materials Today, Dec 2007, 59-60.
Discussion of Reading: “Carbon nanotube-based neat fibers,” Nano Today, Oct 2008, 24-34.
Discussion of Reading: “CNT-Reinforced Ceramics and Metals,” Materials Today, Nov 2004, 44-49.
Discussion of Reading: “Challenges and opportunities for graphene as transparent conductors in optoelectronics,” Nano Today, Dec 2015, 681-700.
Discussion of Video: Polymer Nanotube Composites, Arkema (2009).
Discussion of Video: Blacker than black or NASA (2010) or youtube.
Discussion of Video: Carbon Nanotubes or NOVA "Making Stuff: Stronger" (2011) or youtube.
Discussion of Video: Spinning Carbon Nanotubes or CSIRO (2005) or youtube.
Discussion of Video: Spinning nanotube fibers or Rice University (2014) or youtube.
Discussion of Video: Graphene Revolution or GRAFOID (2015) or youtube.
Discussion of Video: Victor Badminton Rackets (2014) or youtube.
Discussion of Video: CNT Touch-screen (2011) or youtube.
Discussion of Video: Touch-screens from graphene (2015) or youtube.
Skim: "Learning from nature: constructing high performance graphene-based nanocomposites," Materials Today, May 2017, 210-219.
Lab: Prepare for Saturday. Pack your supplies and check signage.
Lab: Continue PMMA Nanospheres - Synthesis of Inverse Opal Photonic Crystals. Load dry sample in boat, add TEOS, put boat in tube furnace.
Lab: Continue PMMA Nanospheres - Optical Diffraction and SEM Determination of Particle Size. Measure visible spectrum and prepare labeled sample for SEM. If you do not see a visible absorption peak, set up another evaporation for a better diffraction result.
Lab: Continue PMMA Nanospheres - Stokes Law measurements. Data needed every 3 or 4 days
Mar 23 Advising Practicum (no class)
Mar 24
(Sat)
Nanodays Topics - Rockford, leave Beloit at 9:00 (meet in lab)
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Mar 26 Class: Soft Lithography and Polymers
Lab notebook due for ZnO Nanorods
Mar 28 Discussion of Reading: Concepts of Nanochemistry, PDMS (Chapter 4).
"Replication of Vertical Features Smaller than 2 nm by Soft Lithography," J. Am. Chem. Soc., 2003, 125 (49), pp 14986.
Lab: PDMS Soft Lithography. (Due Monday) Start this first so PDMS can cure. Do the optical transform and either the CD or DVD. Be sure to use the side with the features as the mold.
Lab: Continue PMMA Nanospheres - Optical Diffraction. If you did a second trial, measure visible spectrum. If you do not see a visible absorption peak, set up another evaporation for a better diffraction result.
Lab: Continue PMMA Nanospheres - Stokes Law measurements. Data needed every 3 or 4 days
Mar 30 Literature reports 3B
1. Christian
2. Zhang
3. Dahlberg
4. Valuck
Outreach reflection due
   
Apr 2 Class: Photovoltaics
Lab notebook due for PDMS Soft Lithography
Apr 4 Discussion of Reading: “Power from the sun,” spie oemagazine, April 2003, pages 24-27.
Discussion of Reading: “Plastic Photovoltaic Devices,” Materials Today, Sept 2004, pages 36-40.
Discussion of Reading: “Inorganic Photovoltaic Cells,” Materials Today, November 2007, pages 20-27.
Discussion of Reading: “Third Generation Photovoltaic Cells,” Materials Today, November 2007, pages 42-50.
Discussion of Reading: “Nanoelectrodes: energy conversion and storage,” Materials Today, June 2009, pages 20-27. (FIRST 4 PAGES.)
Discussion of Reading: “Organic photovoltaics,” Materials Today, Dec 2012, pages 554-562.
Discussion of Reading: “Recent advances in dye-sensitized solar cells,” Materials Today, Apr 2015, pages 155-162.
Discussion of Video: Solar Nanopaint, Nova (2007) or youtube.
Discussion of Video: CuInGaSSe (2007), History Channel or youtube.
Discussion of Reading: “Who Pays for Grid Expansions When Homeowners Generate Their Own Electricity?,” or IEEE Spectrum, 23 Jan 2014.
Discussion of Reading: “Perovskite Solar Cell Bests Bugbears, Reaches Record Efficiency,” or IEEE Spectrum, 7 Jan 2015.
Discussion of Reading: “Millions of Chinese-Made Solar Panels,” Pacific Standard, 30 Jun 2015.
Discussion of Reading: “Ultrathin Solar Cells for Lightweight and Flexible Applications,” or IEEE Spectrum, 26 Aug 2015.
Discussion of Reading: “Graphene and Perovskite Lead to Inexpensive and Highly Efficient Solar Cells,” or IEEE Spectrum, 8 Sept 2015.
Discussion of Reading: “Will Nanophotonics Save Solar Power Tech?,” or IEEE Spectrum, 14 Apr 2016.
Discussion of Reading: “Perovskite Solar Cells Grow Better With a Dash of Acrylic Glass,” or IEEE Spectrum, 19 Sept 2016.
Discussion of Reading: “Perovskites Become More Stable,” or IEEE Spectrum, 29 Sept 2016.
Discussion of Reading: “Tesla to launch solar roofs,” C&E News, 7 Nov 2016.
Discussion of Reading: “Tesla Teams With Tiny Hawaiian Utility to Store Solar,” or IEEE Spectrum, 16 Mar 2017.
Skim: "Use of organic materials in dye-sensitized solar cells," Materials Today, June 2017, 267-283.
Lab: Titanium Dioxide Raspberry Solar Cells Start this first! (due Monday)
Lab: Finish PMMA Nanospheres - SEM Determination of Inverse Opal Hole Size and Inverse Opal Properties. Prepare labeled sample for SEM. Test properties.
Lab: Continue PMMA Nanospheres - Optical Diffraction. If you did a third trial, measure visible spectrum.
Lab: Continue PMMA Nanospheres - Stokes Law measurements. Data needed every 3 or 4 days
Apr 6 Literature reports 3C
1. Simmons
2. Knapp
3. Tumicelli
4. Harrison
   
Apr 9 Quantum Dots
Lab notebook due for TiO2
Apr 11 Discussion of Reading: Concepts of Nanochemistry, CdSe (Chapter 5).
Discussion of Reading: “Quantum dot field effect transistors,” Materials Today, Sept 2013, pages 312-325.
Skim: "Surface ligands engineering of semiconductor quantum dots for chemosensory and biological applications," Materials Today, September 2017, 360-376.
Apr 13 Literature reports 4A
1. Evans
2. Pearlman
3. Kelly
4. Camacho
   
Apr 16 Class: Electrons and Magnetism
Lab notebook due for CdS
Lab notebook due for ZnCuInS
Apr 18 Discussion of Reading: Concepts of Nanochemistry, Iron Oxide (Chapter 6).
Skim: "Robust Magnetic/Polymer Hybrid Nanoparticles Designed for Crude Oil Entrapment and Recovery in Aqueous Environments," ACS Nano, 7(9), 7552-7561 (2013).
Discussion of Audio: Cheap Memory, NPR, January 22, 2012.
Discussion of Video: 3D XPoint Announcement (2015) or Intel.
Discussion of Video: 3D XPoint Memory Technology (2015) or Intel.
Discussion of Reading: Intel Confirms 2016 Arrival Of 3D XPoint (July 2016).
Apr 20 Literature reports 4B
1. Christian
2. Zhang
3. Dahlberg
4. Valuck
   
Apr 23 Class: Scanning Probe Microscopies
Lab notebook due for Emulsion polymerization and size determination of monodispersed polymethylmethacrylate nanospheres. Since this experiment took more than one week, there will be more than one purpose and method, actions and observations, and data sections. Use the combined results in your conclusions.
Apr 25 Spring Day (no class or lab)
Apr 27 Literature reports 4C
1. Simmons
2. Knapp
3. Tumicelli
4. Harrison
   
Apr 30 Class: LEDs and OLEDs
Lab notebook due for Superhydrophobic Cu on Cu
May 2 TEST
Lab: Organic Light Emitting Diodes (due Monday)
Lab: Finish Ferrofluid XRD (due Monday)
May 4 Meet in 447 for AFM Demonstration
   
May 7 Class: Societal Implications
Lab notebook due (Ferrofluid)
Lab notebook due (oLED)
May 9 Discussion of Reading: Concepts of Nanochemistry, Case Histories (Chapter 8).
Discussion of Reading: "Top ten advances in materials science in the last 50 years" by Jonathan Wood, Materials Today, 11(1), 2008.
Discussion of Reading: "The chips are down for Moore's law", Nature, 530, 144–147 (11 February 2016).
Discussion of Reading: "IBM’s Path to 5-Nanometer Transistors", IEEE Spectrum, (5 June 2017).
Discussion of Reading: "Here's Why Nobody's Talking About Nanotech Anymore" (pdf) or Time, Oct 2015.
Discussion of Reading: “A tale of opportunities, uncertainties, and risks,” NanoToday, February 2008, pages 56-59.
Discussion of Reading: “Everyday Uses of Nanotechnology” or C&E News, October 10, 2016.
Discussion of Video: "Are Engineered Nanoparticles Dangerous?" (2016), Andrew Maynard, Risk Innovation Lab, Arizona State University or youtube.
Lab: Cleanup (empty counters and drawers and make sure everything is labeled)

Text

Ludovico Cademartiri and Geoffrey Ozin, Concepts of Nanochemistry, Wiley-VCH (2009), ISBN 978-3-527-32597-9

Literature Sources

Choose a recent nano article from Nanoletters or ACS NANO (or from another journal with approval.) Summarize the paper in a short oral report, focusing primarily on a figure or two in the paper. Be sure to check for supplementary information (movies and the experimental section may be located there). By end of Wednesday email to claim a paper by including a link to the abstract. Papers that have been selected will be posted above. Your article grade will be based on whether you understand the selected material so select something you understand. Test questions in this course will be drawn from these student selected papers, so for the rest of the class your presentation is a practice test.

Nanoletters (American Chemical Society)
ACS NANO (American Chemical Society)

Nano Research (Springer)
Applied Materials and Interfaces (American Chemical Society)
Journal of Nanoparticle Research (Springer)
Nanoscale Research Letters (Springer)
Materials Today (Elsevier)
Materials News (Materials Research Society)
Nanotechnology news stories (PhysOrg)

Basis of evaluation

• Class participation in discussion of text readings.
• Selection of literature article, identification of main figure, and short presentation on article (every 3 weeks).
• Laboratory notebooks (format, most weeks) require you to plan and record your work and also function as weekly problem sets since they involve measurement, calculation, and discussion. What you record in your laboratory notebook will constitute about half the points for this course.
• Reflection on outreach participation (Saturday, March 24).
• Two tests.
Interpret the figures and text from literature reports by expanding on what is being illustrated, explaining procedures or techniques, indicating why it might be important or making connections to our class readings and laboratory work. Tell more than rewriting the caption. Try to use your interpretation to demonstrate additional knowledge beyond what is shown.

Accomodations

If you have a disability and need accommodations, contact Learning Enrichment and Disability Services (LEADS) located on second floor Pearsons (north side), 608-363-2572, learning@beloit.edu or make an appointment through joydeleon.youcanbook.me to get an Access Letter. We can then discuss how your learning needs may be appropriately met. You can also apply for free peer tutoring through the Portal (student life tab, then tutoring forms on the left).

Lab images

Nanodays at Discovery Center


Last modified February 23, 2018 by George Lisensky

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